Cellulose acetate fibers with improved dyeing properties



Patented Apr. 13, 1954 GELLULOSE ACETATE FIBERS WITH IMPROVED DYEING PROPERTIES John R. Caldwell, Kingsport, Tenn, assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application April 1, 1952, Serial No. 279,963

11 Claims. 1

This invention relates to the manufacture of synthetic fibers from the lower fatty esters of cellulose, and more particularly to the manufacture of cellulose acetate fibers having an improved afiinity for acid wool dyes.

In the textile industry it is often desirable to use fibers of different kinds in the manufacture of fabrics. After the fabric has been woven, it may then be subjected to a dyeing operation and it is often desirable that the fibers have dyeing properties which are substantially equivalent. In those fabrics in which cellulose ester fibers are combined with the fibers of natural wool, it has colmnonly been necessary heretofore to employ both an acetate dyestuif and a wool dyestuff to impart color to the fabric. In many cases considerable difficulty has been encountered in matching the shades of the wool fibers and the cellulose ester fibers. In addition, the two types of dyestufi's often respond differently to laundering, light fading, etc. resulting in fabrics having a spotty or irregular appearance after they have been exposed to conditions of wear and clean- Many attempts have been made heretofore to impart properties to cellulose ester fibers so they are receptive to acid type dyes, but the results obtained have not been too: satisfactory. It is thought that the dyeing of wool fibers by acidtype dyestuffs takes place through the reaction of the sulfqnic acid groups in the dye molecule with amine? groups in the wool to form a salt linkage. To impart wooldye afiinity to cellulose ester fibers, compounds have been incorporated therein having basic amino groups, resembling those present innatural wool. In most cases heretofore the fibers which have been so prepared would take up only small amounts of dyestuffs to give a weal; shade, or the dye employed to dye the cellulose ester fibers would show poor stability toward light fading and laundering.

An object of my invention is to prepare fibers of the lower fatty esters of cellulose having good susceptibility to acid dyes and good stability, when so dyed, to fading by light or by laundering.

Another object of the invention is to provide cellulose acetate fibers than can be dyed readily with acid wool dyes. I

Still another object of the invention is to provide compositions containing cellulose acetate and linear polymeric urethanesin an intimate mixture.

Other objects of my invention are apparent hereinafter.

In accordance with the invention. these and other objects are attained by incorporating linear polyurethanes in cellulose ester spinning clones and converting the solution to fibers. The presence of the linear polyurethanes in the fiber imparts acid wool dyeing properties thereto. Fibers prepared in this way can be colored deep shades by acid wool dyes applied by standard methods. It is not necessary to use swelling agents or solvents in the dye bath.

The linear polyurethanes employed in accordance with my invention contain tertiary amine groups which cause the cellulose ester fibers containing them to have a strong affinity for acid Wool dyes. The polyurethanes may be made by reacting triamines containing one tertiary amino group with dichlorocarbonates of glycols. The reaction may be represented by the general equation:

n is 2, 3 or 4, and m is a wholenumber from 20 The amines used in the process are prepared by known methods. 7 For example, a particularly useflul amine is obtained by adding two mols of acrylonitrile to one mol of methyl amine and hydrogenating the twonitrile groups to primary amine groups. The product is methyl bis (gam ma-aminopropyl) amine and has the structure.

The dichlorocarbonates are made by treating lycols with excess phosgene at about 1() C.

The reaction between the dichlorccarbonate and amino compound is carried out in an inert liquid such as benzene, toluene, ethylene dichloride or dioxane. An alkali such as sodium hydroxide, sodium carbonate or calcium oxide is used to combine with the liberated HCl.

The most desirable means of preparing cellulose ester fibers in accordance with my invention is by dissolving the linear polyurethane in the spinning dope which consists of a solution of the cellulose ester in a volatile solvent. Ordinarily the solvent employed for spinning cellulose ester is acetone, and the linear polyurethane may be dissolved therein at the same time the cellulose ester is dissolved. It is-torbe understood, however, thatother solvents such asmethylacetate, methylene chloride, tetra chlorethane, di-

oxane, nitro methane, methyl cellosolve acetate;

diacetone alcohol, methyl ethyl ketone alcohol may be employed for spinning cellulose. esters; and my invention also includes cases using other solvents in which these polyurethanes. are ini-- corporated. To secure optimum afiinitytforrwool.

dyes, the cellulose ester fibers should contain -40% of the linear polyurethane.

My invention is adapted to impart a wooli-dyeing property to the various lower fatty ester acids of cellulose which have been employedifor pro-- paring synthetic fabrics.v For instance, cellulose acetate 'whichzhas been hydrolyzed to a-nacety-l' content of 39 tax-40% .is much employed, especially; in acetone solution. for. making synthetic. fibers.

Also other cellulose esters such as: cellulose. acetate propionateor cellulose acetate butyra-te having a propionate-or butyrate contentof. 1: to 6% such as :describeddnUUS. Patent No.- 2,223,376 may be employed in accordance with the present invention. Also cellulose esters having aneven higher propionate or butyrate-contentmay be employed.- My-invention applies to the fibers prepared from any of these-:celluloseesters=. By, my. invention fibers: are prepared therefrom which are susceptible to-dyeingby anyof the wool dye-- stuffs containingr sulfonic. acid groups in the.- dyemolecules;

'Dhe. following; examples illustrate. my inven.-- tion:

Example I:

Butanediol-1,4 (90 g., 1.0 mol) is mixed with 300g. (3.0 mol) of-phosgene at 'G; and the mixture is allowed to 'Warm upzto room temperature during 8:hours. Excess .phosgene is removed by bubbling a: stream of dryair through. the product. The dichlo-roearbonate isdissolved: in.

20000. benzene. and the-solution is placedin a flask containing 300 cc. water and 2.0 g. sodium;

dodeeyl sulfate The mixture is stirred atabout 10 C. while the following solution is added dropi wise over a period of 30 minutes.

145.0 g. (1.0 mol) methyl bis (gamma-aminopropyl) amine I 90I0g. (2.1 mol) sodium hydroxide 400.0 no. water Thelinear polyurethane separates out as afine powder'that is: isolated by-filtering. It has thestructure:

Eighty g. cellulose acetate (39.4 per cent acetyl) and 20 g. of" the polyurethane are dissolved in 300 g. of acetone. Yarntis spun by the usual dry spinning process. The yarn dyes heavily with. acid wool: dyes.

Example II .Apolyurethane-is prepared from the dichlorocarbonate of. hexanediol-.1-,6 and ethyl bis. (,3,- aminoethyl) amine. It has the structure:

4. Seventy-five g. cellulose acetate and 25 g. of the polyurethane are dissolved in 320 g. of acetone. Yarn spun from the solution dyes heavily with acid wool dyes.

Example III A polyurethaneeis prepared fitom the adichloroearbonateof 2-methyl butanediol-1'A and isopropyl bis (gamma-aminopropyl) amine. It has the structure: (HmoHoufwHmN-Hwo-o-om-on-om-om-o-o0-)".

HC'(OH)2 CH2 Seventy'g:;ofi cellulose acetate and 30 g. of the polyurethane-are: dissolved in 300 g. acetone.

-' Yarn-spunfi'mwthesolution dyes well with acid Wool dyes...

Thefollowing Examples IV and V show the advantage of employing, according to this invention; the linear polyurethanes containing tertiary amino groups over the urethanes not containing tentianyi amino: gronpss:

Example IV (A) Eighty-five grams cellulose :acetate and. 15:

g. of the polyurethane. preparedlin. ExampleL are dissolved infillOTg, acetone. Yam is .spun from the. solution. It.- dyeswell with. acid-.wool, dyes. The yarncontains. 15% of the polyurethane.

B) Aipolyurethane waamade. fi'onnbutanediol; chlorocarbonate. and. gamma-ethylhmino. propyl amine. The polyurethane l iadthe.structurev HM 0Hi ii I -0.0o( om 1-0-0 0- can 7 It isfsiniila'r to thepolyurethane preparedin Exampler'but does noticontairr any tertiary amino groups. Cellulose acetateyarnzcontaining.15% of this polyurethane takes up only one-thirdito one=halfas much acid wool dyeas the yarn'described in (A)..

Emampla V- (A') Gellulose'acetatefiyarn' containing 12% of thezpolyurethane:fitomzExample I1. is spun.

(B) A poly-urethane is made from hexanediol chloroearbonatei. andi hexamethylen'ediamine. Cellulose; acetate yarn containing- 125% of" this product tak esfiup less than. oneehalf as-much acid" woolldye? as the yarir. described 'in (A Any suitabl'eespinningiprdcess may be employed totspin the filaments accordance with: this in'-- vention,.fo1 example, those disclosed in: Stone Patents 2.;000,047 and 2500070485.

The fibers madeby this invention have aevery close resemblance to wool? in: tl'i'eirbehavior to ward acid dyestuffs. Fabrics" made from: wocl incombination: wit'hthe lowerfatty acid esters of cellulose fibers containing 10ito 4'0%'-of the linear polyurethanes describedherein: may be unifomnly dyed in; an acid: type" wool dyebatlr to produce a uniform color, freeof" spots-orirregularities;

What- I claim and desire to 1 secure by Better-s Patent 0f theUnited States is:

1.. Cellulose: ester fibers: having. wool dyeing properties essentially consisting of azl'owerf'atty acid: GStGIJUf 'celluloseihaving 1: to carbon? atoms' and. approximately 1.0.1" to.' 401% by' weight off a linear:polyurethaneihavingi the; generai :for-rnulas:

(HN(OHz),.1 II(CHz),.NHCO-O-X OCO )M whereina R: is an iember:- selected: fronr the.- class: consisting of methyl, ethyl, propyl, isopropyl; and;

butyh. isian alkylene: group selectedf. from. the class consisting of alkylene groups having-1i 2; to;

Groarbcmatomawism smalllwholenumherrfrom 2 to 4, and m is a whole number from 20 to 200.

2. A spinning solution essentially consisting of a lower fatty acid of cellulose having 1 to 4 carbon atoms and approximately to 40% by weight of a linear polyurethane having the general formula:

wherein R is a member selected from the class consisting of methyl, ethyl, propyl, isopropyl and butyl, X is an alkylene group selected from the class consisting of alkylene groups having 2 to 6 carbon atoms, 11. is a small whole number from 2 to 4, and m is a whole number from to 200, dissolved in a low boiling volatile organic solvent.

3. Cellulose ester fibers having wool dyeing properties essentially consisting of a lower fatty acid ester of cellulose having 1 to 4 carbon atoms and approximately 10 to 40% of the linear polyurethane having the formula:

wherein m is a whole number from 20 to 200.

4. Cellulose ester fibers having wool dyeing properties essentially consisting of a lower fatty acid ester of cellulose having 1 to 4 carbon atoms and approximately 10 to 40% of the linear polyurethane having the formula:

wherein m is a whole number from 20 to 200.

5. Cellulose ester fibers having wool dyeing properties essentially consisting of a lower fatty acid ester of cellulose having 1 to 4 carbon atoms and approximately 10 to 40% of the linear polyurethane having the formula:

(HN(CH2)3N(CH2)3NEC O-OCHrOH-OHa-CH|O-C 0-),"

HO(CH3)2 CH3 wherein m is a whole number from 20 to 200.

6. A spinning solution essentially consisting of cellulose acetate and approximately 10 to 40% of the linear polyurethane having the formula:

wherein m is a whole number from 20 to 200 dissolved in acetone.

6 '7. A spinning solution essentially consisting of cellulose acetate and approximately 10 to 40% of the linear polyurethane 'having the formula:

-NH oH2 lI -I(cH2 2NH00-0(0H1)ao0o CrHs wherein m is a whole number from 20 to 200 dissolved in acetone.

8. A spinning solution essentially consisting of cellulose acetate and approximately 10 to 40% of the linear polyurethane having the formula: (HN(OHz)aN(CHz)aNH-OOOOHz?HOHaCH2-OCO-)- NC(CH3)2 CH3 wherein m is a whole number from 20 to 200 dissolved in acetone.

9. Fibers having wool dyeing properties essentially consisting of cellulose acetate and approximately 10 to 40% of the linear polyurethane having the formula.

CHa

wherein m is a whole number from 20 to 200.

10. Fibers having wool dyeing properties essentially consisting of cellulose acetate and approximately 10 to 40% of the linear polyurethane having the formula:

wherein m is a whole number from 20 to 200.

11. Fibers having wool dyeing properties essentially consisting of cellulose acetate and approximately 10 to 40% of the linear polyurethane having the formula:

(HN(CHz)aN(CHn)aNH-CO-O-CHrEH-CHz-CHa-O-CO-h wherein m is a whole number from 20 to 200.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,356,079 Nelles et a1. Aug. 15, 1944 FOREIGN PATENTS Number Country Date 615,884 Great Britain Jan. 13, 1949 

1. CELLULOSE ESTER FIBERS HAVING WOOL DYEING PROPERTIES ESSENTIALLY CONSISTING OF A LOWER FATTY ACID ESTER OF CELLULOSE HAVING 1 TO 4 CARBON ATOMS AND APPROXIMATELY 10 TO 40% BY WEIGHT OF A LINEAR POLYURETHANE HAVING THE GENERAL FORMULA: 